Process of preparing oil-soluble metal soaps



Patented Jan. 29, 1952 PROCESS OF PREPARING OIL-SOLUBLE METAL SOAPSMilton Nowak, Union, N. J., and Alfred Fischer,

Bronx, N. Y., assignors to Nuodex Products Co Inc., Elizabeth", N. J acorporation of New York No Drawing. Application July Serial No. 103,316

17 Claims. (01. 260-414) This invention is directed to the preparationof oil-soluble metal soaps for use in the various arts.

Heretofore such soaps have generally been produced, either throughdouble decomposition processes employing the respective water-solublesalts of the metals and the water-soluble alkali soaps of the particularorganic acids, or, by the reaction of the desired acids with thermallyunstable compounds of the desired metals, such as carbonates, oxidesandthe like. Both of these conventional processes have recognizeddisadvantages. In the commercial practice of the double decompositionprocess, it is impossible to entirely free the end product oil-solublemetal soap from contamination by the lay-product salts of suchreactions, e. g., sodium sulphate. Another drawback to said process isthe need of employing as an intermediate water-soluble salts of thespecific metal. Such salts generally are more costly per metal contentthan the metal itself. Moreover; the equipment required for the practiceof this processis complicated and relatively expensive. The thermaldecomposition process can only be practiced-with certain metals, but notall of them, and the economicsare ad.- verse because the cost of themetal content in the oxides and carbonates and the like is generallyhigher than of the metal itself.

Of the foregoing processes, thedouble decomposition reactions have'commonly been referred to as thewet process and the thermaldecomposition process is known as the dry process.

The object of the present invention is to eliminate the disadvantages ofthe aforesaid conventional processes and to-permit the production of thedesired end products through the use of more simple, highly effi cientand economical process steps. We have beenable to accomplish this resultby a distinctively novel process which we term a hydrous two-phaseacid-metal fusion, wherein the metal in comminuted form is reacted atelevated temperature with free organic acid in the presence of water.

An acid to be suitable within the teachings of this invention, must becapable of yielding waterinsoluble, oil-soluble normalmetal soaps.Examples of such acids are oleic acid, tall oil acids, naphthenic acids,-2-ethylhexoi'c acid, petroleum sulphonate acids, nonanoic acid, linseedoil fatty acids, soya bean oil fatty acids, phenyl stearic acids, andether acids, such as butoxy butyric acid, etc. For commercial reasons,especially economic reasons and quality considerations, we prefer to usenaphthenic acid, tall oil acid and z ethylhexoic acid, singly. orcombination, but

we wish it to be understood that the scope of this invention iscommensurate with the entire range of those substantiallywater-insoluble and substantially oil-soluble organic acids capable offorming oil-soluble heavy metal soaps.

While we are particularly concerned with the preparation of heavy metalsoaps, we have also obtained satisfactory results with other metals,such as aluminum, strontium and the like. Among the heavy metals whichare of especial commercial importance, we have satisfactorily used:lead, cobalt, manganese, iron, copper, zinc, nickel, but we have alsocarried out preparation with many other members of the group of heavymetals.

Speaking generally, the process of this invention employs the metalpreferably in powder form, in order that a large surface per weight isexposed to the reaction. The metal, together with the selected organicacidand water, is maintained at elevated temperatures while thoroughagitation is maintained. Under such conditions, there is a very completeand rapid conversion of the metal into the corresponding metal soap.According to this invention, it is necessary to have water presentthroughout the entire reaction. This can be accomplished in variousways. For example, the process maybe carried out under appropriaterefluxing conditions. At the end of the reaction period, which incommercial practice may be a matter of a few hours, it is usuallydesired to remove the water. This can be accomplished by distilling itoff or by mechanical means, e. g., centrifuging. In many instances, wehave found it desirable to employ water immiscible solvents for the endproduct. We have used mineral spirits, xylol and the like which areincluded within the reaction mass. The presence of such solvents oftenhelps to facilitate the reaction and to reduce the viscosity of the endproduct, thus improving manipulation. In some cases, the reactionproceeded indifierently to the presence or absence of air, while inother cases the presence or absence of air aifected the velocity of thereaction. p

It is sometimes desirable to employ certain modifying agents in minoramounts in order to impart certain characteristics to the end products.For example, the use of addition agents in amounts of as little as 1%may reduce the viscosity of the end product, which is desirable forcertain applications. Moreover, certain of these agents serve to preventoxidation and thus instability of the end product. The agents referredto may also be efiective in improving the com- (1611561381161 an airinlet tube.

or after the reactions of this invention as they 7 play no part inthereaction but are useful in modifying the properties of the end preducts.

Having thus generally described the present invention, we will nowproceed with specific examples of practical performance.

EXAMPLE 1 Cobalt naphthenate y A solution of 530' grams of crudenaphthenic acid (acid number 228) in 720 grams of mineral spirits ischarged in a 2 1iter, 3-neck, round bottom flask, equipped withagitator, reflux con- The solution is agitated, and 0 grams of wateradded, together with 63 grams of-fine y powdered cobalt metal (95%cobalt content). The reaction mixture is heated to 195 F. and air isblown into the mix ture at a rateof 25.liters;per hour.

. After 10 hours, the reaction is complete. The air inlet tube isclosed, the reuflx condenser removed, and the water present driven offby heating the reaction mixture to 220 F. Thesolution is then filteredto eliminate siliceous matter, analyzed for percent oil-soluble -cobalt,and diluted with mineral spirits to 6% cobalt. A

V conversion'of 95% of the metal is obtained.

EXAMPLE 1a Cobalt naphthenate A portion of the end product obtained inEx ample lis stripped ofits volatile solvent by distillation invacuum.The endproduct obtained is thus essentially free ofany solvent and is asolid at room temperature. 7 a

, 1b Cobalt naphthenate with additives V A cobalt naphthenate isprepared in exactly the same manner as described in Example 1, ex

cept that modifying agents are added to the end product reaction mass.Specifically 10 grams of triethanolamine lactate and 10 grams of amylacid phosphate are added to the end products after the reaction iscompleted and prior to the drivingoff of the water. The addition ofthese modifying agents results in a cobalt naphthenate end product whichis adapted for more universal use. The viscosity of the end product andresist ance to oxidation are considerably improved over that of thestraight cobalt naphthenatee'nd prod act of Example 1. 7

EXAMPLE 2 Cobalt 'tallate A solution of 325grarns of a commercial gradeof tall oil (acid number 183, rosin acids content 37%) is dissolved in310 grams of toluol, and charged in a 2 liter, B-neck, round bottomflask,

- equipped with agitator;refiuxvcondenser, and an air inlet tube. Thesolution is agitated, and 50 grams of water added with 31.5 grams offinely V powdered cobalt metal cobalt content). The reaction mixture isheated to 195 F. and air is blown into the mixture at a rate of 0.8liter per minute. 7

After 12 hours, the reaction is complete. The water present is distilledoff in-vacuo, the solution filtered, analyzed, and diluted with toluolto 4% cobalt metal content. The yield is 720 grams (a conversion of 96%of the metal).

The end product is a dark violet colored liquid consisting of a solutionof cobalt tallate in'toluol, and may be employed as a drying catalyst inpaintsand varnishes.

, EXAMPLE 3 Cobalt Z-ethyl heroate 350 grams of 2-ethyl hexoic acid(acid number i and placed in a 3 liter, 3-neck, round bottom flask,equipped with agitator, reflux condenser, and an air inlet tube. Thesolution is agitated vigorously, while 100. grams of water are added,together with 64.4 grams of powdered cobalt metal (92% cobalt content).The reaction mix' ture is heated to 175 F. and air passed into'themixture at the rate of 0.6 liter per minute. After 8 hours, the reactionis complete.

The water present is then distilled oii, and t 2 solution filtered toremove siliceous matter originally present in the cobalt metal. Thesolution is then analyzed, and diluted with mineral spirits to yield 728grams of a solution of cobalt z-ethyl hexoate containing .8% cobalt (97%conversion EXAMPLE 4 Manganese Z-ethyl hemoate 380 grams of 2-ethylhexoic acid (acid number 380) are mixed-with grams mineral spirits, andplaced in a 3 liter, 2-neck, round-bottom flask, equipped with agitatorand reflux condenser. 60 grams of manganese metal flakes ofapproximately 4 mesh particle size are added to the solution, togetherwith 60 grams water. The mixture is agitated rapidly, while heating to212 F. The reaction is allowed to continue until all of the manganesemetal has dissolved (approximately 10 hours).

The water present is then distilled ofi completely, together with someof the mineral spirits.

685. grams or a commercial grade of tall 011 (acid number 184, rosinacids content 37%), are mixed with 130 grams mineral spirits, and placedin a 3 liter, 2- neck, round bottom flask, equipped with agitator andreflux condenser. 60 grams of manganese metal powder (particle size: 98%through 300 mesh screen) are added to the solution, together with 60grams of water. The mixture is agitated rapidly, while heating to 212 F.The reaction is-allowed to continue until all of the manganese metal hasdissolved (approximately 2 hours).

The water present is then distilled off completely, together with someof the mineral spirits. The material is analyzed and diluted withmineral spirits to exactly 6% manganese metalcontent. iA y'ield'of 984grams of manganese tallate solution of.6'% metal content is obtained.

f This product is a dark amber liquid, and is useful as a catalyst inthe drying of paints and varnishes'. 1

" Manganese nonanoate 361- grams of nonanoi'c-acid (acid number 345) aremixed with 130 grams mineral spirits, and placed in a 3 liter, 2-neck,round bottomflask, equipped with agitation, and reflux condenser. 60grams-of manganese metal powder (particle size; 98% through 300 meshscreen) are added to the solution; together with 60 grams of water. Themixture is agitated rapidly, while heating to 212 F. The reaction isallowed to continue un til all of the manganese metal has dissolved(approximately 2 hours) I H The water present is then distilled oflcomplete ly, together with some of the mineral spirits. There is thenadded grams of nonanoic acid for the. purpose of adjusting the viscosityand stability characteristics of the end product. The material isanalyzed and diluted with mineral spirits to exactly 6% manganese metalcontent. A yield of 985 grams of manganese nonanoate solution of 6%metal content is obtained (98.5% yield).

This product is a dark amber liquid, and is useful as aa catalyst in thedrying of paints and varnishes.

EXAMPLE 7 M anganese naphthenate d ill grams rectified naphthenic acid(acid number 230) are mixed with 130 grams mineral spirits, and placedin a 3 liter, 2-neck, round bottom flask, equipped with agitator andreflux condenser. grams of manganese metal powder (particle size: 98%through 300 mesh screen) are. added to the solution, together with 60grams of water. The mixture is agitated rapidly, while heating to 212 F.The reaction is allowed to continue until all of the manganese metalhasdissolved. (approximately 2 hours).

The-water present is then distilled ofl completely, together with someof the mineral spirits. The material is analyzed and diluted withmineral spirits to exactly 6% manganese metal content.- A yield of 986grams of manganese naphthenate solution of 6% metal content is obtained.(98.6% yield.)

This product is a dark amber liquid, and is use-' ful asa catalyst inthe drying of paints and varnishesm.

"EXAMPLE7a Manganese naphthenate with additive ?Bll leale y ea i ss s irnd .i ro salsni 6, of general performance over that of the 'end productof'Example U @Instead of using the particular additive referred to, wehave also used as an additive, amyl acid phosphate, triethylcitratatributyl citrate, etc. with satisfactory commercial results.

EXAMPLE 8 copper oleate"" 785 grams oleic acid (acid number 195) aredissolved in 600 grams mineral spirits, and placed in a 3-liter. roundbottom flask, equipped with agitato'nmeflux condenser, and-an air inlettube. 100 grams-water and grams powdered copper metal (particle size:98% through 325 mesh screen are .added to the acid solution and thereaction mixture thenagitated. rapidly. Temperature or the mixture isbrought to 212 F. and air :bubbled in at the rate of approximately 30:")liters per hour. 1 1

After 14 hours, the reaction is substantially complete. The water isdistilled from the mixture in vacuo, together with some of the mineralspirits. The reaction mixture is then filtered and analyzed for metalcontent. After analysis, it..is diluted with mineral spirits to yield900 grams .of a solution of copper oleate containing 8% copper metal.

- This product is a bright dark green liquid. It is useful as apesticide in the preservation of celiulosic materials, as canvas, wood,etc.

EXAMPLE!) .Oopper naphthemte 665 grams crude naphthenic acid (acidnumber 228) are dissolved in 600 grams mineral spirits, and placed in a3 liter, round bottom flask, equipped with agitator, reflux condenser,and an air inlet tube. 100 grams water and 80 grams powdered coppermetal (particle size: 98% through 325 mesh screen) are added to the acidsolution; and reaction mixture then agitated rapidly. Temperature of themixture is brought to 212 F. and air bubbled in at the rate ofapproximately 300 liters per hour.

"After li hours, the reaction is substantially complete. The water isdistilled from the mixture in vacuo, together with some of the mineralspirits. The reaction mixture is then filtered and analyzed for metalcontent. After analysis, it is diluted with mineral spirits to" yield930 grams of a solution of coppernaphthenate containing 8% copper metal.

The product is a' bright dark green liquid. It is useful as a pesticidein the preservation of cellulosic materials, as canvas, woods, etc.

EXAIVLPLE 10 Copper'tallate 840 grams of .a commercial grade of tall oil(acid number 183, rosin acids content 37%) are dissolved in 600 gramsmineral spirits, and placed in a 3-liter, round bottom flask, equippedwith agitator, reflux condenser, and an air inlet tube. 100 grams waterand 80 grams powdered copper metal (particle size;- 98% through 325 meshscreen) are added to .the acid solution and reaction mixture thenagitated rapidly. Temperature ofthe mixture is brought. to 210 F and airbubbled in at the rate 30(l liters per hour.;

After 14 hours-the reaction is substantially 99 3191 1 The .wa er 1 d stled from. the mixture in vacuo, together with some of the mineral ofapproximately 9 metal (particle size: 98% passingffthrough 300 meshscreen) are added, and the reaction mixture rapidly agitated. Thetemperature of the mixture is kept at 212 F. while air is blown mat themixing of pigments, and as a pesticide and fungicide for thepreservation of cellulosic ma terials.

EXAMPLE 18 Lead naphthenate 244 grams rectified naphthenic acid (acidnumber 230) are dissolved in 300 grams mineral spirits and solutionplaced in a 2 liter flask, equipped with reflux condenser, agitator andair inlet tube. 60 grams of water and 103.5 grams of finely powderedlead metal (particle size: 98% passing through 200 mesh screen) are thenadded to the reaction mixture and the entire mixture agitated rapidlyand maintained at temperature of 212 F. Air is blown in at the rate of90 liters per hour. After 12 hours, reaction is complete. 4

Water is distilled from the reaction mixture in vacuo, and the residuefiltered and analyzed for lead content. After analysis, the solution isdiluted with mineral spirits to exactly 16% lead metal content. Aconversion of 97% of the metal is obtained.

This product consists essentially of a solution of neutral lead soap ofnaphthenic acid, and is an amber liquid. This material may be used as adrying catalyst in paints and varnishes.

EXAMPLE 19 Basic lead naphthenate 1'77 grams of rectified naphthenicacid (acid number 230) are dissolved in 150 grams mineral spirits, andplaced in a 1 liter flask, equipped with reflux condenser, agitator, andair inlet tube. 60 grams of water, and 103.5 grams finely powdered leadmetal (particle size: 98% passing through 200 mesh screen) are added tothe reac. tion mixture, which is then rapidly agitated, and heated to atemperature of 212 F. Air is blown in at the rate of 3 liters per minutefor a period of hours, after which time the reaction is EXAMPLE 20 Basiclead tallate 122 grams of a refined grade of tall oil (acid number 183,rosin acids content 37%) are dis:

solved in 150 grams mineral spirits, and placed in a 1 liter flask,equipped with reflux condenser,

agitator, and air inlet tube. 60 grams of water, and 103.5 grams finelypowdered lead metal (particle size 98% passing through 200 mesh screen)are added to the reaction mixture, which is then rapidly agitated, andheated to a temperature of 212 F. Air is blown in at the rate of 3liters perminute for a period of 15 hours, after which time thereactionis found to be substantially complete.

The water present is then distilled irom the reaction mixture in vacuo.The remaining solu-- tion is then filtered and analyzed for leadcontent. After analysis, it is diluted with mineral spirits to yield 610grams of a solution containing 16% lead metal:

This end product consists of a solution of basic lead tallate in mineralspirits. It is a clear light amber liquid, and is useful as a dryingcatalys for paints and varnishes.

EXAMPLE 21 Lead Z-ethyl hexoate 148 grams Z-ethyl hexoic acid (acidnumber 380) are dissolved in'300 grams mineral spirits and solutionplaced in a 2 liter flask, equipped with reflux condenser, agitator, andair inlet tube. 60 grams of water and 103.5 grams of finely powderedlead metal (particle size: 98% passing through 200 mesh screen) are thenadded to the reaction mixture and the entire mass agitated rapidly andmaintained at temperature of 212 F. "Air is blown in at the rate ofliters per hour. After 12 hours, reaction is complete.

Water is distilled from the reaction mixture in vacuo, and theresiduefilteredand analyzed for lead content. After analysis, thesolution is diluted with mineral spirits to exactly 24% lead metalcontent. A- conversion 01' 97% of the metal is obtained.

This product consists essentiallyof'a solution of. a neutral lead soapof2-ethy1 hexoic acid, and is an amber liquid. This material maybe usedas a drying catalyst in paints and varnishes.

EXAMPLE 22 Cobalt salt of a combination of tall oilcnd naphthenic acidAfter 10 hours the reaction is. complete. The

air inlet tube is closed, the reflux, condenser re moved, and the waterpresentdriven off by heat-, ing the reaction mixture to 220 F. Thesolution is then filtered toeliminate siliceous mat.-, ter, analyzed forper cent soluble cobalt, and diluted with mineral spirits to 6% cobalt.A conversion of 96% of the metal is obtained. r

The end product is a dark blue-violet liquid consisting of asolutionof-cobalt naphthenate tallate 'in mineral spirits, andcontaining 6% cobalt. This material is useful as a catalyst in thedrying of film-formingoxidizable material, as paints, varnishes, andthe. like.

1 1 EXAMPLE 23 Manganese-salt of a combination of z-eth'yl heroic agcidand naphthenic acid solved (approximately hours).

The water present is then distilled off completely, together with someof the mineral spirits. The material is analyzed and diluted withmineral spirits-to exactly 6% manganese metal content. A conversion of99% of manganese metal is obtained.

This product is a dark amber liquid, and is useful as a catalyst in thedrying of paints and varnishes' EXAIVIPLE 24 Lead-(cobalt naphthenate261grams rectified naphthenic acid (acid numher 230) are dissolved in300 grams mineral spirits, and placed in a 2 liter flask, equipped with.reflux condenser, agitator, and air inlet tube. To this solution areadded '70 cc. water, 11.2 grams finely powdered cobalt metal (cobaltcontent 92%) (particle size: 98% passing through 325 mesh screen), and103.5 grams of finely powdered lead metal (particle size: 98% passingthrough 200 mesh screen). The mixture is agitated rapidly, andmaintained at a temperature of 212 R,

. while blowing in air. at the rate of 4 liters per minute. After hours,the reaction is substantially complete. r

The water is distilled off in vacuo, and the reaction mixture thenfiltered and analyzed for per cent soluble lead and cobalt. Afteranalysis, it

is diluted with mineral spirits to a lead content of 16% and a cobaltcontent of 1.6%. The conversion of each metal is approximately 93%.

' The end product is a deep violet colored liquid, containing lead andcobalt in the ratio of 10:1; this ratio is one commonly employed wheresuch metal combinations are used as drying catalysts in paints andvarnishes.

EXAMPLE.

Lead-cobalt salt of z-ethyl heroic acid as naphthenic acid 177 gramsrectified naphthenic acid (acid numher 230) and 51 grams 2-ethyl hexoicacid (acid number 380) are dissolved in 300 grams mineral spirits, andplaced in 2,2 liter flask, equipped with reflux condenser, agitator, andair inlet tube. To

' this solution are added 70 cc. water, 11.2 grams is diluted withmineral spirits to a lead content 01' 16% and a cobalt content of 1.6%.The conversion of each metal is approximately 96%..

The end product is a deep violetcolored liquid, containing lead andcobalt in the ratio of 10:1; this ratio is one commonly employed wheresuch metal combinations are used as drying catalysts in paints andvvarnishes. I

'It will be apparent from the foregoing examples that a single acid anda single metal may be reacted .in the manner stated or combinations ofacids and/or metals may also be satisfactorily carried out. Theinvention is not limited to the illustrative examples given.

The end-products of this invention are suitable for many uses. They arehighly satisfactory when used as catalysts for the. drying of oxidizablefilm-forming materials, such as paints, var

nishes and the like. They are also very effective as drying catalystsfor printing inks. Another important field of application, particularlyfor the copper soaps, is that of pest control, including theconservation of wood and other cellulosic materials against the ravagesof insects, fungi, etc. The end products may also be employed ascoloring agents, e. g., as constituents of plastic compositions, toimpart certain desirable color ization. Still another important utilityis that of stabilizing certain plastics, such as vinyl plastics againstdecomposition. It is also quite prac- I tied] to employ the heavy metalsoapsthemselves The foregoing examples refer to "naphthenie 7 acid,""tall oil acid" and tall oil. The raw materials so designated are theraw materials of the trade and all of such raw materials so sold on theopenmarket will function properly in the ex;

amples given for the purpose of carrying out the present invention.

Having thus fully described the invention,

what we: claim as new and desire to secure by Letters Patent is:

l. The herein described hydrous two phase metal-acid fusion-processwhich comprises: com-'- mingling at least one comminuted polyvalenlimetal, at least one organic acid capable of form ing oil-soluble heavymetal soaps, and a quantity of waterto produce a reaction mass, andheating said mass to efi'ect reaction thereof to a temperature above 100F. under conditions to maintain the water in its liquid phase throughoutthe reac tion while agitating the mass.

2. Process as claimed in claim 1, which includes the freeing of theoil-solublemetal soap end product from the water at the conclusion ofthe reaction.

3. The process of claim 1, wherein one metal is a heavy metal.

4 The processof claim 1, wherein one metal is a heavy metal and one acidis naphthenic' acid.

5. The process of claim 1, wherein one metal is cobalt and one acid isnaphthenic acid.

I 6. The process of claim 1, wherein one metal is cobalt and one acid istall 011 acid.

-7. The process of claim 1, wherein one metal is cobalt and one acid is2-ethylhexoic acid.

8. The process of claim 1, wherein one metal. is manganese and one acidis naphthentic acid.

9. The process of claim 1, wherein one metal is, manganese and one acidis tall oil acid.

10. ..The process of claim 1, wherein one metal is manganese and oneacid is 2-ethylhexoic acid...

. .llgjlfhe process- 01' claim 1, wherein one. metalv isiron' andoneacid is naphthenic acid. 12. The process of claim 1, wherein the metalis iron and one acid is tall oil acid. I

13. The process or claim 1, wherein the metal is iron and one acid is2-ethy1hexoic acid.

14. The process of claim 1, wherein the metal is copper and one acid isnaphthenic acid.

15. The process of claim 1, wherein the metal is copper and one acid istall oil acid.

16. The process of claim 1, wherein the metal is copper and one acid is2-ethylhexoic acid.

17. The herein described hydrous two-phase metal-acid fusion processwhich comprises: commingling at least one comminuted polyvalent metal,at least one organic acid capable of forming oil-soluble heavy metalsoaps, and a quantity of water to produce a reaction mass, and heatingsaid mass in the presence of air to effect reaction thereof to atemperature above 100 F. under conditions to maintain the water initsliquid phase throughout the reaction while agitating the mass.

MILTON NOWAK. ALFRED FISCHER.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 2,338,128 Minich Jan. 4, 19442,397,767 Taylor Apr. 2, 1946 2,409,678 Hamblet Oct. 22, 1946 2,416,074Weber et a1 Feb. 18, 1947 2,423,619 Roon July 8, 1947 2,445,935 BondiJuly 27, 1948 2,472,424 Hoover June 7, 1949 2,527,789 Bondi Oct. 31,1950 FOREIGN PATENTS Number Country Date 589,242 Great Britain June 16,1947

1. THE HEREIN DESCRIBED HYDROUS TWO-PHASE METAL-ACID FUSION PROCESSWHICH COMPRISES: COMMINGLING AT LEAST ONE COMMINUTED POLYVALENT METAL,AT LEAST ONE ORGANIC ACID CAPABLE OF FORMING OIL-SOLUBLE HEAVY METALSOAPS, AND A QUANTITY OF WATER TO PRODUCE A REACTION MASS, AND HEATINGSAID MASS TO EFFECT REACTION THEREOF TO A TEMPERATURE ABOVE 100* F.UNDER CONDITIONS TO MAINTAIN THE WATER IN ITS LIQUID PHASE THROUGHOUTTHE REACTION WHILE AGITATING THE MASS.